JP4722954B2 - Adhesive for printed wiring board and method for producing adhesive layer for printed wiring board - Google Patents

Description

The present invention relates to an adhesive and an adhesive layer, and in particular to provide an adhesive for printed wiring boards and an adhesive layer that are excellent in toughness without reducing heat resistance, electrical insulation, and chemical stability. Suggest a technology.

  In recent years, printed circuit boards and wiring boards on which LSIs are mounted are required to have high density and high reliability by a fine pattern corresponding to miniaturization or speeding up of electronic equipment as the electronics industry advances.

Therefore, recently, as a method of forming a conductor on a wiring board, an adhesive is applied to the substrate surface to form an adhesive layer, the surface of the adhesive layer is roughened, and then electroless plating is performed. The additive method of forming conductors is attracting attention.
According to this method, a conductor is formed by performing electroless plating after resist formation. Therefore, the wiring with high density and high pattern accuracy is lower in cost than the etched foil method (subtractive method) in which pattern formation is performed by etching. There is a feature that can be produced.

  In such an additive method, as a means for improving the adhesion between the conductor and the adhesive layer (hereinafter described as “peel strength”), chemical etching is conventionally performed on the conductor forming surface side of the adhesive layer. There is known a method of providing fine irregularities due to the above.

  However, in recent additive-type printed wiring boards that require wiring with higher density and higher pattern accuracy, an anchor formed by roughening the surface of the adhesive layer is further added in order to form a fine resist pattern with high accuracy. It is necessary to make it smaller. Therefore, when the anchor is made small, the fracture area is reduced, resulting in a problem that the peel strength is remarkably lowered.

On the other hand, in the fields related to automobiles / transportation equipment, electrical / electronic parts, machinery-related fields, household goods-related fields, civil engineering / architecture fields, and medical fields, metal parts have been replaced with plastics due to recent improvements in engineering plastics. It's getting on.
For example, a camera housing or a fixing ring using polycarbonate or a bearing made of polyacetal may be used. Furthermore, gears made of ultra high molecular weight polyethylene have been developed.

However, these resin parts may need to be coated with a metal film on the surface of the parts in terms of design, corrosion resistance, wear resistance, and the like. In such a case, as a means for coating the metal surface on the resin surface, conventionally, there has been proposed a method in which an adhesive layer is provided on the surface of the resin substrate, the surface of the adhesive layer is roughened, and then the metal film is coated. Has been.
For example, in Japanese Patent Publication No. 58-44709, an electroless plating adhesive composed of acrylonitrile butadiene rubber and an epoxy resin is applied to the surface of an insulating substrate, and then the epoxy resin portion on the surface of the adhesive layer is dissolved and removed. A method for obtaining a metal film coating by electroless plating after surface roughening is disclosed.
JP-A-61-276875 discloses that an electroless plating adhesive in which a heat-resistant resin fine powder is dispersed in a heat-resistant resin matrix is applied on a substrate, and then the heat-resistant resin fine powder is applied. A method of electroless plating after roughening the surface by treating with an oxidizing agent is disclosed.

  However, engineering plastics (substrate resin) coated with a metal film via an adhesive layer may generate cracks due to a difference in thermal expansion coefficient between the substrate resin and the adhesive layer during a heat cycle, There was a problem that the adhesive layer itself was cracked.

  In order to solve such various problems, there is a method of increasing the strength of the heat-resistant resin matrix constituting the coating metal or the adhesive. However, according to the experiments by the inventors, in the prior art using copper as the coating metal and a thermosetting resin or a photosensitive resin as the heat-resistant resin matrix constituting the adhesive, the electroless plating that forms the coating metal It was found that peeling of the film was caused by destruction of the heat resistant resin matrix. That is, it has been found that the cause of the decrease in the adhesion strength is insufficient strength of the heat-resistant resin matrix constituting the adhesive. Furthermore, it was found that the cause of cracks generated during heat cycles and cracks was also due to insufficient strength on the heat resistant resin matrix side.

Therefore, in order to solve the above-mentioned various problems of the prior art, the main object of the present invention is to constitute an adhesive for printed wiring boards without deteriorating heat resistance, electrical insulation, and chemical stability. To strengthen the heat-resistant resin matrix,
Another object of the present invention is to provide a method for producing an adhesive layer for a printed wiring board that is excellent in adhesion to a coated metal.

  As a result of diligent research regarding the improvement of the strength of the heat-resistant resin matrix constituting the adhesive, the inventors have made some functional groups photosensitive as the heat-resistant resin matrix constituting the adhesive. An uncured thermosetting resin containing a resin substituted with a group and / or a mixed resin of an uncured photosensitive resin and a thermoplastic resin, and further curing the resin composite is used as an adhesive layer. As a result, it has been found that even when the anchor depth formed by the roughening treatment is small, it is possible to provide a metal film adherend such as a printed wiring board having excellent adhesive strength with a conductor metal, and the present invention has been conceived.

That is,
(1) configuration of a printed wiring board adhesive of this invention, the heat-resistant resin matrix in uncured, before curing the heat-resistant resin matrix and compatible, and after curing phase separation to the acid or oxidizing In an adhesive formed by mixing an epoxy-modified CTBN resin solution that can be dissolved and removed by an agent, the heat-resistant resin matrix is an epoxy resin as an uncured thermosetting resin and / or an uncured photosensitive resin . a resin mixture of a polyethersulfone as the epoxy acrylate and a thermoplastic resin, with the resin mixture forms a resin complex by the curing process, the resin composite of the melting removable CTBN resin is cured to distribute in the sea of the heat-resistant resin matrix consisting of the body into an island shape, and characterized by comprising a resin mixture was adjusted the compatibility of its To do.
The resin mixture is preferably dissolved in a solvent to be in a compatible state or incompatible state.
When the resin mixture is in a compatible state, when Ru is cured this, by adjusting the curing rate and the phase separation rate, to obtain quasi-homogeneous compatible structure to be described later, co-continuous structure, the spherical domain structure Can do.
On the other hand, when this resin mixture is in an incompatible state, a spherical domain structure can be obtained by curing it as it is.
In the present invention, “dissolution removal” refers to dissolution and decomposition of particulate matter by chemical action using a roughening solution such as acid, alkali, oxidizing agent, water, and organic solvent. is there.
In the present invention, the “thermosetting resin and / or resin mixture of photosensitive resin and thermoplastic resin” refers to (i). A resin mixture of a curable resin and a thermoplastic resin, (ii). A resin mixture of a photosensitive resin and a thermoplastic resin, or (iii). Means a resin mixture of a thermosetting resin, a photosensitive resin and a thermoplastic resin

(2) The structure of the method for producing an adhesive layer for a printed wiring board according to the present invention is a method for producing an adhesive layer having a roughened surface for a printed wiring board, which is provided on a substrate for a printed wiring board. Further, by curing the adhesive for printed wiring board, the heat-resistant resin matrix made of the cured resin composite, wherein the dissolved and removable CTBN resin is in the sea of the heat-resistant resin matrix. Forming a heat-resistant resin matrix dispersed in islands to form a sea-island structure, and dissolving and removing the CTBN resin from the surface of the heat-resistant resin matrix made of the cured resin composite, A roughened surface is formed , and the resin composite preferably has a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure.
Here, the resin that can be dissolved and removed is compatible with an uncured heat-resistant resin matrix before curing, phase-separated with the resin matrix in the curing process, and non-uniform with the resin matrix after curing. In such a state, a resin that forms a “sea-island structure” is used.
Phase separation in the course of curing is (i). Those that cause phase separation upon curing of the matrix resin, (ii). (Iii) those which cause phase separation by curing both the matrix and the resin to be dissolved and removed; The phases were separated by heat (temperature) added during curing, which phase is fixed by curing, there is.
In the present invention, the “sea-island structure” means that the heat-resistant resin matrix is the sea, and in this sea, the concentration of the resin having a high concentration of the resin that can be dissolved and removed exists in an island shape. It means a uniform state and the boundary between the sea and the island is unclear. The islands may be independent in the sea, or the islands may be continuous.

The structure of the metal film adherend using the adhesive layer for a printed wiring board according to the present invention has an adhesive layer having a roughened metal coating side on the substrate, and the roughened adhesive layer. In the case where a metal film is provided on the conversion surface, this adhesive layer is preferably formed from the resin composite described in (2) above .

That is, this printed wiring board adhesive layer is made of a heat-resistant resin matrix comprising a resin composite of a thermosetting resin and / or a photosensitive resin and a thermoplastic resin, in which a resin that can be dissolved and removed is cured. It is desirable to form an island-island structure dispersed in islands in this sea, and this resin composite should form a quasi-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure Is preferred.
Here, as the dissolution-removable resin, hardening before compatible with heat-resistant resin matrix of uncured, and process the resin matrix and phase separation in the curing, after curing and the resin matrix not A resin that forms a “sea-island structure” in a uniform state is used .
In addition, as said base | substrate, the thing of various shapes which can be used industrially including the board | substrate containing the printed wiring board in which the conductor circuit was formed, fiber shape, rod shape, and spherical shape can be used.

In the above-mentioned metal film adherend using the adhesive layer for a printed wiring board according to the present invention, a substrate is used as a substrate, and the coated metal is etched as necessary, or the metal is coated in a pattern shape Becomes a printed wiring board.
Such printed wiring board, on a base plate, dissolved removable resin, the hardened thermostable resin matrix consisting of resin composite of a thermosetting resin and / or a photosensitive resin and a thermoplastic resin An adhesive layer that is dispersed in an island shape in the sea to form a sea-island structure is provided, and a roughened surface is formed on the conductor forming surface of the adhesive layer, and A conductor circuit is provided on the roughened surface, and the heat-resistant resin matrix is composed of a thermosetting resin and / or a resin composite of a photosensitive resin and a thermoplastic resin. The resin composite has a resin structure of any one of a pseudo-homogeneous compatible structure, a co-continuous structure, and a spherical domain structure.

As described above, the adhesive for printed wiring boards of the present invention is a thermosetting resin and / or a resin mixture of a photosensitive resin and a thermoplastic resin as its heat-resistant resin matrix, and is quasi-uniform by a curing process. compatible structure, so as to form a resin complex having any of the resin structure of co-continuous phase structure or spherical domain structure, using what the compatible state is being adjusted, and, in the resin mixture, solvent release It is composed of a dispersion of resin that can be removed, and such an adhesive is cured under appropriate curing conditions to form a sea-island structure, a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure. Therefore, it is possible to form a resin composite having any of the following resin structures, toughen the resin matrix without lowering the heat resistance, electrical insulation and chemical stability. The adhesion between the adhesive layer and the coating metal can be significantly improved.
As a result, it is possible to stably provide various metal film adherends for printed wiring boards and other industrial parts that are excellent in peel strength even in wiring with higher density and higher pattern accuracy.
In other words, not only for printed wiring boards but also in the automobile industry, it is applied to various parts such as disc brake bodies, clutch hubs, fuel injection nozzles, fuel transport pipes, gears, etc. In the electrical and electronic industries, lead frames and hermetic seals Application to ceramic packages, connectors, capacitors, resistors, solar electrodes, hard disks, etc., in the industrial machinery industry, to construction materials such as pumps, valves, heat exchangers, filters, screws, dies, bearings, decorative plates, etc. It can be applied to various structural materials and parts coated with a metal film, which is industrially beneficial.

(1) The printed wiring board adhesive of the present invention is characterized in that the resin matrix constituting the adhesive is an uncured thermosetting resin and / or a resin mixture of an uncured photosensitive resin and a thermoplastic resin. The compatibility of the resin mixture is adjusted so as to form a resin composite having a resin structure of either a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure by a curing treatment. the heat-resistant resin matrix cure is that a dissolve removable resin are dispersed.
In particular, in the printed wiring board adhesive of the present invention, it is desirable that the resin mixture is uniformly mixed in a compatible state.
Thereby, the resin matrix of the said adhesive agent can be toughened, without reducing heat resistance, electrical insulation, and chemical stability.

  Here, the reason why the above-described compatible resin mixture is used as the heat-resistant resin matrix of the adhesive is that a resin composite composed of a thermosetting resin and / or a photosensitive resin and a thermoplastic resin obtained by curing. This is because the resin structure of the body can be easily controlled by the curing conditions.

As a method for uniformly mixing and dispersing an uncured thermosetting resin and / or an uncured photosensitive resin and a thermoplastic resin in a compatible state, a method of dissolving the resin in a solvent, or heating by heating. There is a method of mixing a thermosetting resin or a photosensitive resin after melting a plastic resin. Especially, the method of dissolving resin in a solvent is used suitably. This is because the workability is good and the resin can be dissolved at a low temperature.
Examples of the solvent include dimethylformamide (DMF), normal methylpyrrolidone (NMP), methylene chloride, diethylene glycol dimethyl ether (DMDG), and the like.

In the adhesive of the present invention, the heat-resistant resin matrix has an uncured thermosetting resin and / or a blending ratio of the uncured photosensitive resin and the thermoplastic resin of 15 to 50 wt% in terms of the thermoplastic resin content. It is desirable that
The reason for this is that if the thermoplastic resin content is less than 15 wt%, the toughness of the adhesive layer cannot be improved, while if it exceeds 50 wt%, it is difficult to apply, and a smooth and uniform adhesive. This is because it becomes difficult to form a layer.

  The viscosity of the adhesive of the present invention is desirably 0.5 to 10 Pa · s as measured at 25 ° C. The reason for this is that if it exceeds 10 Pa · s, the leveling property is lowered and a smooth adhesive surface cannot be obtained. On the other hand, if it is less than 0.5 Pa · s, the particulate matter that can be removed by dissolution or decomposed is settled. This is because a sufficient roughened surface cannot be obtained, and the adhesion with the coated metal is lowered.

(2) A feature of the method for producing an adhesive layer for a printed wiring board of the present invention is that a resin composite formed by curing the adhesive described in (1) under appropriate curing conditions is used. is there. Thereby, the adhesive bond layer excellent in adhesiveness with a covering metal can be provided stably.

  Here, the reason why a thermosetting resin and / or a resin composite of a photosensitive resin and a thermoplastic resin is used as the heat-resistant resin matrix of the adhesive layer is that when the resin composite is used, the thermosetting resin or the photosensitive resin is used. As a result, the toughness of the entire resin matrix can be strengthened without lowering the heat resistance, elastic modulus, electrical insulation, and chemical stability. It is because it can plan.

Although the surface of the adhesive layer for printed wiring boards produced by the method for producing an adhesive layer for printed wiring boards of the present invention is roughened, the roughened surface can be dissolved and removed dispersed in islands. It is formed by a so-called cocoon-shaped recess formed by dissolving and removing a resin. Therefore, in this recess, a metal film such as electroless plating is deposited and becomes an anchor, and the resin matrix constituting the recess has high toughness and does not easily break down the resin. The adhesion strength (peel strength) can be maintained high without peeling from the roughened surface.
Further, since the above heat-resistant resin matrix is excellent in toughness, it is not easily broken even when the adhesive layer itself undergoes deformation, and can be used even when the substrate is subjected to deformation or stress.

The resin composite in the method for producing an adhesive layer for a printed wiring board according to the present invention has a resin structure of any one of a pseudo-homogeneous compatible structure, a co-continuous structure, and a spherical domain structure. here,
(a) The quasi-homogeneous compatible structure is a particle of constituent resin particles in a resin composite of a thermosetting resin or a photosensitive resin and a thermoplastic resin showing a phase diagram of a so-called LCST type (Low Critical Solution Temperature). This means that the diameter is 0.1 μm or less as measured by transmission electron microscope observation, and the glass transition temperature peak value of the resin is one by dynamic viscoelasticity measurement. This state is close to an ideal mixed state of the resin, and is a new concept that the inventor has devised independently. Here, the dynamic viscoelasticity measurement conditions in the present invention are a vibration frequency of 6.28 rad / sec and a temperature rising rate of 5 ° C./min.
In other words, this pseudo-homogeneous compatible structure exceeds the physical properties specific to thermoplastic resins such as polyethersulfone (PES) while maintaining the physical properties specific to thermosetting resins such as epoxy resins or photosensitive resins such as acrylic resins. It has a more homogeneous structure showing the introduction effect, and the interaction between the thermosetting resin or photosensitive resin and the thermoplastic resin is extremely strong.
The structure of such a resin composite can be seen from the fact that even when the fracture surface of the resin composite is etched using a solvent that dissolves the thermoplastic resin, the surface state is almost unchanged from that before etching.
The resin composite that forms such a quasi-homogeneous compatible structure has a higher fracture strength and tensile strength than those of the respective constituent resins alone.

  Such an effect of the structure of the resin composite is particularly remarkable when the content of a thermoplastic resin (for example, PES) in the composite is 15 to 50 wt% in solid content. The reason for this is that if the thermoplastic resin content is less than 15 wt%, the thermoplastic resin molecule entangled in the resin component network is small, so that the toughening effect is not fully exhibited, while the thermoplastic resin content is 50 wt%. This is because if the percentage exceeds 50%, the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin becomes small due to a decrease in the crosslinking point.

  Such a quasi-homogeneous compatible structure is obtained by dissolving an uncured thermosetting resin or an uncured photosensitive resin and a thermoplastic resin in a solvent as required and mixing them uniformly, and then increasing the curing speed. And / or by slowing the phase separation rate, the particle diameter of the constituent resin particles is set to 0.1 μm or less as measured by a transmission electron microscope.

  Specifically, as the first method, when a thermosetting resin is used, one or more selected from the curing temperature of the thermosetting resin, the type of the curing agent, and whether or not photosensitivity is imparted. On the other hand, when a photosensitive resin is used, the photocuring factor of the photosensitive resin, such as an initiator, a sensitizer, a photosensitive monomer, exposure conditions, etc. There is a method of curing at a curing rate exceeding the quasi-homogeneous phase formation point determined by The quasi-homogeneous phase formation point here is the lower limit of the curing rate at which a quasi-homogeneous compatible structure in which the particle size of the resin particles constituting the composite is 0.1 μm or less as measured by TEM observation can be obtained. means.

  In addition, as a second method, the quasi-homogeneous phase formation point determined by any one or more factors of the number of functional groups or the molecular weight in one molecule of the uncured thermosetting resin or uncured photosensitive resin is exceeded. There are methods to cure at no phase separation rate. The quasi-homogeneous phase formation point here is the upper limit of the phase separation rate at which a quasi-homogeneous compatible structure in which the particle size of the resin particles constituting the composite is 0.1 μm or less as measured by TEM observation can be obtained. Means.

  Further, as a third method, there is a method of curing at a curing rate exceeding the quasi-homogeneous phase formation point and at a phase separation rate not exceeding the quasi-homogeneous phase formation point. This means a method in which factors that determine the cure rate and phase separation rate interact with each other.

Next, the interrelation between the various factors described above that determine the curing rate or phase separation rate will be described. First, regarding the factors that determine the curing rate, if other factor conditions are constant,
(i) The higher the curing temperature of the thermosetting resin, the faster the curing rate.
Therefore, when the thermosetting resin is cured beyond the lower limit value of the curing temperature necessary to obtain a curing rate exceeding the pseudo-homogeneous phase formation point, the resulting resin composite has a pseudo-homogeneous compatible structure.
(ii) The curing rate becomes faster as the curing agent has a shorter gelation time.
Therefore, when the thermosetting resin is cured using a curing agent that does not exceed the upper limit of the gelation time necessary to obtain a curing rate exceeding the pseudo-homogeneous phase formation point, the structure of the resulting resin composite is pseudo. It becomes a homogeneous compatible structure.
(iii) The curing speed increases as the photosensitivity is imparted.
Therefore, in a combination in which other factor conditions form a pseudo-homogeneous compatible structure, the resulting resin composite has a more homogeneous pseudo-homogeneous compatible structure by imparting photosensitivity to the resin.
In addition, as a method for imparting photosensitivity, there are a method of introducing a photosensitive group into a thermosetting resin or a thermoplastic resin, and a method of blending a photosensitive monomer, and a photoinitiator and a photosensitizer as necessary. May be blended.
A photosensitive resin such as an acrylic resin can be used instead of the thermosetting resin. In this case, it is necessary to cure the photosensitive resin at a curing rate exceeding the quasi-homogeneous phase formation point determined by a photocuring factor such as an initiator, a sensitizer, a photosensitive monomer, and exposure conditions.
However, in the case of imparting photosensitivity to the thermosetting resin, or in the case of adding a photosensitive monomer in order to improve the resolution of development, an uncured thermosetting resin and / or an uncured photosensitive resin And the thermoplastic resin become less compatible, causing phase separation even at relatively low temperatures (see FIGS. 10 to 12). Therefore, when adding photosensitivity to a thermosetting resin or adding a photo-sensitive monomer, the adhesive is vacuum-dried at low temperatures (30-60 ° C) as necessary, and this is exposed and cured once. Then, by performing thermosetting (80 to 200 ° C.), a pseudo-homogeneous compatible structure can be obtained.

  In consideration of such facts, when there is only one kind of the above-mentioned variation factor in the combination of the thermosetting resin or the photosensitive resin and the thermoplastic resin, the value of that factor corresponding to the quasi-homogeneous phase formation point is determined by one point. . Therefore, when there are two or more types of the above-mentioned variation factors, various combinations of the values of the factors corresponding to the quasi-homogeneous phase formation point are conceivable. That is, it is possible to select a combination that exhibits a curing rate such that the particle diameter of the constituent resin particles is 0.1 μm or less as measured by TEM observation.

Next, regarding the factors that determine the phase separation rate, if other factor conditions are constant,
(i) The greater the number of functional groups in one molecule of the uncured thermosetting resin or uncured photosensitive resin, the less likely phase separation will occur (the phase separation rate will slow down).
Therefore, an uncured thermosetting resin or an uncured photosensitive resin having a number of functional groups in one molecule exceeding the lower limit of the number of functional groups in one molecule necessary for obtaining a phase separation rate not exceeding the pseudo-homogeneous phase formation point. When cured using, the structure of the resulting resin composite becomes a quasi-homogeneous compatible structure.
(ii) The greater the molecular weight of the uncured thermosetting resin or uncured photosensitive resin, the less likely phase separation will occur (the phase separation rate will be slower).
Therefore, the resin composite obtained when cured with an uncured thermosetting resin or uncured photosensitive resin having a molecular weight exceeding the lower limit of the molecular weight necessary to obtain a phase separation rate that does not exceed the quasi-homogeneous phase formation point The body structure is a pseudo-homogeneous compatible structure.

  In consideration of such facts, when there is only one kind of the above-mentioned variation factor in the combination of the thermosetting resin or the photosensitive resin and the thermoplastic resin, the value of that factor corresponding to the quasi-homogeneous phase formation point is determined by one point. . Therefore, when there are two types of variation factors, various combinations of the factor values corresponding to the quasi-homogeneous phase formation point are possible. That is, it is possible to select a combination that exhibits a phase separation rate such that the particle diameter of the constituent resin particles is 0.1 μm or less as measured by TEM observation.

In such a quasi-homogeneous compatible structure of the resin composite, an epoxy resin can be used as the thermosetting resin, and it is desirable to use an epoxy resin having an epoxy equivalent of about 100 to 1000. The reason for this is that it is difficult to produce an epoxy resin having an epoxy equivalent of less than 100. On the other hand, if it exceeds 1000, it is difficult to mix with a thermoplastic resin such as PES, and the Tg point is lowered to make it harder to cure. This is because phase separation is likely to occur during heating, and a pseudo-homogeneous compatible structure is difficult to obtain.
The molecular weight of the epoxy resin is preferably 200 to 10,000. The reason for this is that when the molecular weight of the epoxy resin is less than 200, a sufficient reaction rate cannot be obtained, and even if cured, the cured product becomes too hard and brittle. This is because the compatibility is lowered.
Moreover, although PES can be used as a thermoplastic resin, it is desirable that the molecular weight of this PES is 3000 to 100,000. This is because if the molecular weight of PES is less than 3000, the effect of improving toughness due to the pseudo-homogeneous compatible structure cannot be obtained. On the other hand, if it exceeds 100,000, a compatible state with a thermosetting resin or a photosensitive resin cannot be formed. Because.

  As described above, the resin composite exhibiting a pseudo-homogeneous compatible structure has specific physical properties exhibited by thermosetting resins such as epoxy resins or unique physical properties exhibited by photosensitive resins such as acrylic resins, and PES. The physical property value higher than the original physical property of the thermoplastic resin such as can be exhibited. That is, the PES-modified epoxy resin and the PES-modified acrylic resin according to the present invention are higher than the resin strength of PES alone, and have a toughening effect of an epoxy resin or an acrylic resin that has not existed before.

(b). A co-continuous structure means a composite structure in which spherical particles rich in thermosetting resin such as epoxy resin are present in a matrix rich in thermoplastic resin such as PES (Takashi Inoue) Et al., POLYMER, 30, p662 (1989)).
When the fracture surface of such a resin composite is etched using a solvent that dissolves the thermoplastic resin, the matrix portion rich in the thermoplastic resin dissolves, and only spherical particles such as connected epoxy resin are observed. I know from that.
The resin composite that forms such a co-continuous structure is a tougher resin than a thermosetting resin alone such as an epoxy resin because a thermoplastic resin having excellent toughness exists as a continuous phase.

(c) The spherical domain structure mainly refers to a structure in which spherical domains made of a thermosetting resin or a photosensitive resin are uniformly dispersed independently from each other in a resin matrix of a thermoplastic resin.
The structure of the resin composite is such that when the fracture surface is etched using a solvent that dissolves the thermoplastic resin, the thermoplastic resin-rich matrix portion dissolves, and the thermosetting resin is uniformly dispersed independently. Only spherical particles are observed.
The resin composite that forms such a spherical domain structure is tougher than the thermosetting resin alone, because spherical particles of the thermosetting resin are dispersed in the “sea” of the thermoplastic resin. It becomes resin.

  Such an effect of the co-continuous structure and the spherical domain structure of the resin composite is particularly remarkable when the content of the thermoplastic resin (for example, PES) in the composite is 15 to 50 wt% in solid content. The reason for this is that if the thermoplastic resin content is less than 15 wt%, the thermoplastic resin molecule entangled in the resin component network is small, so that the toughening effect is not fully exhibited, while the thermoplastic resin content is 50 wt%. This is because if the percentage exceeds 50%, the interaction between the thermosetting resin or the photosensitive resin and the thermoplastic resin becomes small due to a decrease in the crosslinking point.

  In such a resin composite, it is desirable that the average particle size of the spherical particles constituting the co-continuous structure or the spherical domain structure is more than 0.1 μm and not more than 5 μm. This is because when the average particle diameter of the spherical particles is 0.1 μm or less, it is difficult to form a co-continuous structure or a spherical domain structure, whereas when it exceeds 5 μm, the toughness cannot be improved. In addition, the photosensitive characteristics and heat resistance are also lowered.

The above-mentioned bicontinuous structure or spherical domain structure is (i) controlling the substitution rate between the functional group and the photosensitive group involved in the thermosetting of the thermosetting resin, or (ii) the type of the photosensitive resin, The molecular weight is adjusted, and the uncured thermosetting resin and / or uncured photosensitive resin and thermoplastic resin are mixed in a compatible or incompatible state, and then dried or cured. By adjusting the average particle size, the average particle size of the spherical particles to be formed exceeds 0.1 μm and is 5 μm or less.
Further, a thermosetting resin and / or a photosensitive resin may be used as the resin matrix, and a thermoplastic resin may be used as a resin that forms a spherical domain that is connected to or independent of each other.

As described above, the printed wiring board adhesive layer produced by the method for producing an adhesive layer for printed wiring board of the present invention is a resin having a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure. It is desirable that the resin composite be formed from a resin composite having a structure, and in particular, a resin having a higher resin strength can be obtained by forming from a pseudo-homogeneous compatible structure than from a co-continuous structure or a spherical domain structure. Therefore, it is more preferable to form a pseudo-homogeneous compatible structure as a resin matrix of the adhesive layer.

In addition, as for the adhesive layer for printed wiring boards manufactured by the manufacturing method of the adhesive layer for printed wiring boards of this invention, it is desirable that the thickness is 10-200 micrometers. The reason for this is that when the thickness of the adhesive layer is less than 10 μm, the adhesion strength (peel strength) decreases, whereas when it exceeds 200 μm, it is difficult to remove the solvent in the adhesive, and drying and curing are difficult. It is difficult.

Wherein the printed wiring board adhesive layer metal film adherend used according to the invention has an adhesive layer which is roughened on the surface of the substrate, and the metal on the roughened surface of the adhesive layer In the metal film adherend provided with a film, the adhesive layer is a resin composite as described in (2) above, that is, any one of a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure. It is in the point formed with a resin structure.

Printed circuit board for the adhesive layer according to the present invention, although its surface is roughened, the roughened surface may be dissolved removable resin is dissolve removal of dispersed like islands, so-called octopus pot It is formed by a concave portion. Therefore, in this concave portion, a coating metal such as electroless plating is deposited and becomes an anchor, and the resin matrix constituting the concave portion has high toughness and does not easily break the resin. The adhesion strength (peel strength) can be maintained high without peeling from the roughened surface.

In the metal film adherend using the adhesive layer for a printed wiring board according to the present invention, a substrate is used as a substrate, and the coated metal is etched into a pattern or coated in a pattern, can do. Moreover, such a printed wiring board can also be multilayered.
In this case, the roughened surface is preferably R _max = 1 to 20 μm. This is because if the thickness is less than 1 μm, the adhesion strength between the coating metal and the adhesive layer is reduced, and if it exceeds 20 μm, it becomes difficult to produce a printed wiring board having a fine pattern with a pattern interval of 100 μm or less.

  According to such a printed wiring board, the heat-resistant resin matrix constituting the adhesive can be toughened without lowering the heat resistance, elastic modulus, chemical stability, and electrical insulation, so that the higher It is possible to stably provide a wiring board having excellent peel strength even in wiring with high density and high pattern accuracy.

Above in the manufacturing method of the described such printed wiring board adhesives and adhesive layer, the thermosetting resin used in the heat-resistant resin matrix, amino resins such as phenol resins, melamine resins and urea resins, epoxy resins, epoxy Modified polyimide resin, unsaturated polyester resin, polyimide resin, urethane resin, diallyl phthalate resin and the like can be used. This is because these resins are excellent in thermal and electrical characteristics. As this thermosetting resin, one in which a part of functional groups contributing to thermosetting is partially substituted with a photosensitive group can be used, and for example, an epoxy resin 5-70% acrylate is preferable.

  The thermoplastic resin used in the heat-resistant resin matrix is polyethersulfone (PES), polysulfone (PSF), phenoxy resin, polyetherimide (PEI), polystyrene, polyethylene, polyarylate, polyamideimide, polyphenylene sulfide, polyether ether. Ketone, polyoxybenzoate, polyvinyl chloride, polyvinyl acetate, polyacetal, polycarbonate and the like can be used. This is because these thermoplastic resins have high heat resistance and are tough, and can be compatible with the thermosetting resin by using a solvent.

Especially, it is suitable that the thermosetting resin and thermoplastic resin which were mentioned above are an epoxy resin and polyether sulfone (PES), respectively.
The reason for this is that an epoxy resin, which is a component of the resin matrix, and PES are mixed and dispersed in a solvent such as methylene chloride and dimethylformamide, and a pseudo-homogeneous compatible structure, a co-continuous structure, and a spherical domain structure can be easily formed. is there.
In addition, when using a mixed system of epoxy resin and PES, the PES-modified epoxy resin forms a pseudo-homogeneous compatible structure, so that the matrix is toughened, and the tensile strength and tensile elongation are both of the epoxy resin alone. It was found to improve more than 1.5 times. Furthermore, due to the toughening of the resin matrix, even when the anchor depth is the same, the peel strength of the electroless plating film in the printed wiring board using the adhesive or adhesive layer of the present invention is only epoxy resin as the resin matrix. Inventors confirmed that it became high compared with the case where it used.

In the present invention, as the thermosetting resin and / or the thermoplastic resin described above, a resin provided with a photosensitive group or a resin to which a photosensitive resin or monomer is added can be used.
The reason for this is that, in the case of a resin composite having a pseudo-homogeneous compatible structure, by adding a photosensitive group to a thermosetting resin or the like, the thermosetting resin is cured in a short time by exposure and phase separation does not proceed. This is because they can be combined, and as a result, a pseudo-homogeneous compatible structure can be easily formed. On the other hand, in the case of a resin composite having a co-continuous structure or a spherical domain structure, the shape (particle size, etc.) of the particles in the co-continuous structure or the spherical domain structure can be easily controlled.

  In the present invention, a photosensitive resin can be used instead of adding a photosensitive group to a thermosetting resin or the like. As such a photosensitive resin, those having 1 to several unsaturated double bonds in the molecule such as acryloyl group, methacryloyl group, allyl group, vinyl group can be used. Epoxy acrylate, polyester acrylate, polyether acrylate , Silcon acrylate, polybutadiene acrylate, polystilethyl methacrylate, vinyl / acryl oligomer (copolymerized with branched acid, acid anhydride, hydroxy group, glycidyl group monomer and vinyl or acrylic polymer, then acrylic monomer Reaction product), polyethylene / thiol (a copolymer of olefin and mercaptan) and the like are preferably used.

  Here, as a photoinitiator that is important as a photocuring factor of this photosensitive resin, benzoisobutyl ether, benzyldimethyl ketal, diethoxyacetophenone, acyloxime ester, chlorinated acetophenone, hydroxyacetophenone, etc. , Benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, and intramolecular hydrogen abstraction type such as isobutylthioxanthone are preferably used.

  Photoinitiators include triethanolamine, Michler's ketone, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4 Any one or more of isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, polymerizable tertiary amine and the like are used.

As the sensitizer, Michler's ketone, Irgacure 651, isopropylthioxanthone and the like are suitable, and some of the above photoinitiators act as sensitizers.
The composition ratio of the photoinitiator and the sensitizer is, for example, with respect to 100 parts by weight of the photosensitive resin.
Benzophenone / Michler's ketone = 5 parts by weight / 0.5 parts by weight Irgacure 184 / Irgacure 651 = 5 parts by weight / 0.5 parts by weight Irgacure 907 / Isopropylthioxanthone = 5 parts by weight / 0.5 parts by weight is preferred.

  As the photosensitive monomer or photosensitive oligomer constituting the photosensitive resin, epoxy acrylate, epoxy methacrylate, urethane acrylate, polyester acrylate, polystyryl methacrylate and the like are preferably used.

  As the curing agent for the resin matrix of the present invention, when an epoxy resin is used as the thermosetting resin, an imidazole-based curing agent, diamine, polyamine, polyamide, organic acid anhydride, vinylphenol, or the like can be used. On the other hand, when a thermosetting resin other than an epoxy resin is used, a known curing agent can be used.

Next, the sea like an island dispersed dissolved removable resin used in the heat resistance resin matrix that are used in the present invention will be described in detail.

Sea islands in dispersed dissolved removable resin used in the heat resistance resin matrix, as such resins, hardening before is compatible with the heat-resistant resin matrix of uncured, after curing the resin matrix And a resin that forms a “sea-island structure” in a non-uniform state with a resin matrix .
The resin such as this, there is a thermoplastic resin such as rubber-based resin, a polyester elastomer such as the aforementioned butadiene and ABS resin. For example, a rubber-based resin is soluble in a phase solvent of an uncured heat-resistant resin matrix, but is not compatible with the uncured heat-resistant resin matrix itself, and an uncured region (island) where the concentration of the rubber-based resin is high It is formed in a heat-resistant resin matrix (sea) and exhibits a non-uniform concentration state (sea-island structure).
In such a resin liquid forming the “sea-island structure”, it is difficult to control the size of the “island”, and it is difficult to manage the quality. In this respect, it is disadvantageous in terms of mass production as compared with a resin that does not require a curing treatment such as a pre-cured resin, inorganic or metal particles that can control the particle diameter by classification or the like and easily manage the quality.
Furthermore, in order to make the uncured heat-resistant resin matrix have a quasi-homogeneous compatible structure, the curing conditions must be adjusted. Also in this respect, if there is an uncured resin liquid as described above, it is disadvantageous because the conditions for curing the resin liquid must be adjusted.
However, since the resin liquid that forms the “sea-island structure” does not contain solid components such as resin, inorganic particles, and metal particles that have been previously cured, kneading time can be reduced, and the adhesive solution It is excellent in that it can be easily prepared.
Further, since the viscosity can be easily reduced, the coating film is excellent in smoothness and leveling.
Note that it is instead dissolve removable resin, also be used curing treated heat resistant resin powder soluble in acid or oxidizing agent.
This heat-resistant resin powder becomes insoluble in a diluting solvent that dissolves a thermosetting resin, a photosensitive resin, or a thermoplastic resin by a curing process. By reducing the viscosity of the resin solution with this diluting solvent, the curing process is performed. This is because the above-described heat-resistant resin powder is uniformly dispersed in the resin solution.
Also, when obtaining a resin composite having a quasi-homogeneous compatible structure, a solvent is used to mix the thermosetting resin or photosensitive resin in a compatible state with the thermoplastic resin. Since the above heat-resistant resin powder does not dissolve in the solvent, a clear anchor can be formed.
The reason why it is desirable to be soluble in acids and oxidants is that oxidants have a strong decomposability, can form clear anchors in a short time, have excellent productivity, and are formed by this oxidant. This is because the adhesive layer having the anchors is hardly dissolved or deteriorated under a normal use environment. On the other hand, acid does not require neutralization treatment as found in oxidizers, is economical, and waste liquid treatment is easier than oxidizers, making it easier to install and safer. It is because it is excellent in property. As the heat resistant resin powder, epoxy resin, amino resin (melamine resin, urea resin, guanamine resin), polyester resin, bismaleidotriazine resin and the like can be used.

In this invention, the particulate material can be used in various shapes such as a spherical shape, a hollow shape, and a crushed piece shape, and in particular, (1) particles having an average particle size of 10 μm or less, (2) powder having an average particle size of 2 μm or less Agglomerated particles having an average particle size of 2 to 10 μm, (3) a mixture of a powder having an average particle size of 2 to 10 μm and a powder having an average particle size of 2 μm or less, and (4) an average particle size of 2 to 10 μm It is desirable to select from pseudo particles obtained by adhering at least one selected from a powder having an average particle size of 2 μm or less or an inorganic powder having an average particle size of 2 μm or less to the surface of the powder. This is because when the average particle size exceeds 10 μm, the anchor becomes deep and it becomes impossible to form a so-called fine pattern of 100 μm or less, while the aggregated particles of (2), the mixture of (3) or (4) The reason why quasi-particles are desirable is that complex anchors can be formed and peel strength can be improved.
In order to prevent aggregation of the particulate matter, it is desirable that the surface thereof is coated with silica sol or the like.
The amount of the particulate material is desirably 5 to 100 by weight with respect to the resin solid content 100 of the heat-resistant resin matrix. The reason is that when the weight ratio is less than 5, the anchor cannot be formed, and when it exceeds 100, kneading becomes difficult, and the amount of the heat-resistant resin matrix is relatively reduced, and the adhesive layer It is because the intensity | strength of falls.

In the present invention, an epoxy resin is used as a thermosetting resin component constituting a heat-resistant resin matrix that is hardly soluble in a roughening solution such as an acid or an oxidizing agent, while a roughening solution such as an acid or an oxidizing agent is used. An epoxy resin powder can also be used as a heat-resistant resin powder that is soluble in water. This will be described below by taking the solubility in an oxidizing agent as an example.
Epoxy resins can have their physical properties greatly different by controlling the type of prepolymer (a relatively low molecular weight polymer having a molecular weight of about 300 to 10,000), the type of curing agent, and the crosslinking density.
This difference in physical properties is not an exception to the solubility in the oxidizing agent, and (i) the backbone structure of the monomer and the curing agent, (ii) the crosslinked structure, and (iii) the crosslinking density can be arbitrarily selected to achieve any solubility. Can be adjusted. (i) and (ii) are the main factors, and (iii) is used as a secondary factor.
Here, as for the skeleton structure of the monomer, generally, the aliphatic epoxy has the highest solubility, and then the solubility decreases most in the glycidylamine type and glycidyl ether type.
As for the crosslinked structure, for example, the hydroxy ether structure obtained by the reaction of epoxide and amine has particularly high solubility, and the solubility is particularly lowered in the ether structure in which epoxide is reacted with imidazole as a curing catalyst.
The crosslink density decreases as the epoxy equivalent increases, and as a result, the solubility increases.
The decrease in solubility is achieved by polyfunctionalizing the epoxy monomer. In the phenol novolac type, the solubility decreases as the monomer repeating unit n increases from 0 to 1 and 2 in order.
Therefore, based on the solubility difference with respect to the oxidizing agent, for example,
As an “oxidizing agent-soluble epoxy resin” constituting the heat-resistant resin powder,
(A) “Epoxy resin that is gently crosslinked using an aliphatic epoxy as the epoxy prepolymer, an aliphatic amine curing agent as the curing agent, and having an epoxy equivalent of about 265” is used.
On the other hand, as “the epoxy resin that is hardly soluble (including insoluble) in the oxidizing agent” as the thermosetting resin component of the heat-resistant resin matrix, (B) “bisphenol A type epoxy resin is used as the epoxy prepolymer” , An epoxy resin with an aromatic diamine-based curing agent as the curing agent and an epoxy equivalent of around 170 ”, or a lower solubility than this (C)“ Phenol novolac type epoxy resin as the epoxy prepolymer and curing An epoxy resin having an epoxy equivalent of about 136 using an imidazole curing agent as the agent is used.
Moreover, the said epoxy resin (B) can also be used as "an epoxy resin soluble in an oxidizing agent". In this case, the said epoxy resin (C) is used as "an epoxy resin hardly soluble in an oxidizing agent".

As can be understood from the example described above, whether the acid or oxidizing agent is soluble or hardly soluble (or insoluble) depends on the relative dissolution rate of the acid or oxidizing agent in the roughing solution. It means a difference. In other words, a resin that is soluble in a roughening solution such as an acid or an oxidizing agent, or an insoluble resin powder that has a difference in solubility may be arbitrarily selected. Incidentally, the means for giving a difference in solubility to the resin is not limited to (i) the kind of prepolymer, (ii) the kind of curing agent, and (iii) the adjustment of the crosslinking density, but other means are Also good.
Table 1 lists the prepolymer, curing agent, epoxy equivalent, and relative value of solubility for each of the aforementioned epoxy resins.

  In the present invention, a roughening treatment with an oxidizing agent or the like for a certain period of time is performed using the solubility difference of each epoxy resin as described above. By performing such a treatment, the soluble epoxy resin fine powder having the highest solubility in the oxidizing agent or the like is vigorously dissolved, and a large recess is formed. At the same time, an epoxy resin matrix containing a thermoplastic resin hardly soluble in an oxidizing agent or the like remains, and a roughened surface (anchor) as shown in FIG. 1 is formed.

  In the present invention, as the heat-resistant resin matrix, a thermosetting resin such as an epoxy resin mixed with a thermoplastic resin such as PES is used. By containing a thermoplastic resin in this way, acid or The tendency for the solubility with respect to an oxidizing agent etc. to fall was seen. In particular, when a resin composite having a quasi-homogeneous compatible structure was employed as the heat resistant resin matrix, the decrease in solubility was significant.

Next, the manufacturing method of the layer metal film to-be-adhered body using the adhesive agent and adhesive layer of this application is demonstrated.
(i). First, an adhesive mainly composed of an adhesive of the present invention, a so-called uncured thermosetting resin and / or a resin mixture of an uncured photosensitive resin and a thermoplastic resin, is applied to a substrate, or An adhesive layer is provided by laminating a film obtained by semi-curing the adhesive itself, or by forming the substrate itself with the adhesive. Further, the adhesive layer is dried and cured to form an adhesive layer in which the resin composite constituting the resin matrix has a resin structure of any one of a pseudo-homogeneous compatible structure, a co-continuous structure, and a spherical domain structure.

Here, examples of the substrate include the following metals, resins, and paper, which are formed into a predetermined shape.
(Magnetic medium)
Polyethylene terephthalate film, hard magnetic disk (electromagnetic shield)
Filter paper (automobile)
Disc brake body, disc brake piston, clutch hub, oil pump cam, mission gear shaft (industrial machine)
Screws and bearings (electrical and electronic industries)
Printed wiring boards, semiconductor mounting boards (building materials)
Phenolic resin impregnated core paper

(ii). Next, at least part of the “island-like resin in the sea-island structure ” dispersed on the surface of the adhesive layer is made using a roughening liquid such as an acid, an oxidant, an alkali, water, or an organic solvent. Dissolve and remove .
As a method using the above roughening solution, the substrate on which the adhesive layer is formed can be immersed in the roughening solution, or the substrate can be sprayed with the roughening solution. The surface of the adhesive layer can be roughened.
Examples of the oxidizing agent include chromic acid, chromate, permanganate, and ozone, and examples of the acid include hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, and organic acid.
As the alkali, sodium hydroxide, sodium carbonate, potassium hydroxide, ammonia and the like are preferable.
Examples of the organic solvent include methyl ethyl ketone, benzene, toluene, dioxane, acetone, trichloroethylene, ethylene dichloride, carbon disulfide, ethyl acetate, butyl acetate, tetrahydrofuran, cyclohexanone, nitroethane, pyridine, chloroform, and carbon tetrachloride.

The relationship between the island-shaped resins in the sea -island structure and the roughening solution for removing them will be described.
For elastomers such as rubber-based resin, chromic acid, a mixture of chromic acid and sulfuric acid, chromates, permanganates, oxidizing agents such as ozone it is suitable as roughening solution.

(iii). Next, a metal film is coated on the surface-roughened adhesive layer on the substrate.
Examples of the method for coating the metal film include electroless plating, electrolytic plating, and sputtering.
Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating, and electroless silver plating. Particularly, electroless copper plating, electroless nickel plating and It is preferable that at least one of electroless gold plating, electroless cobalt-nickel-phosphorous plating, and electroless copper-nickel-phosphorous plating. In addition, after performing the electroless plating, a different kind of electroless plating or electroplating may be performed, or solder may be coated.
In the electroless plating, various patterns can be drawn by plating by forming a plating resist or the like.
Alternatively, electroless plating may be applied to the entire surface and then etched. Further, the metal to be deposited by a method such as sputtering includes Cu, Ni, Cr, Ti, Mo, Au, or alloys thereof.

  The metal film adherend manufactured in this way is applied to various parts such as a disc brake body, a clutch hub, a fuel injection nozzle, a fuel transport pipe, a gear in the automobile industry field, and in the electric and electronic industry field. Application to lead frames, hermetic seals, ceramic packages, connectors, capacitors, resistors, solar electrodes, hard disks, etc. In the industrial machinery industry, applications to pumps, valves, heat exchangers, filters, screws, dies, bearings, etc. Is possible.

Next, a method for producing a printed wiring board as the metal film adherend will be described.
(i). First, a substrate is used as a substrate, and this substrate is mainly composed of the adhesive of the present invention, so-called uncured thermosetting resin and / or a resin mixture of uncured photosensitive resin and thermoplastic resin. An adhesive layer is provided by applying an adhesive, laminating a film obtained by semi-curing the adhesive itself, or forming the substrate itself with the adhesive. Further, the adhesive layer is dried and cured to form an adhesive layer in which the resin composite constituting the resin matrix has a pseudo-homogeneous compatible structure, a co-continuous structure, or a spherical domain structure.

(ii). Then, the dispersed though that sea surface of the adhesive layer - at least a portion of the island-shaped resin in an island structure, dissolved dividing removed by using acid or oxidizing agent, alkali, water, a roughening solution such as an organic solvent you.
As a method of using the above roughening solution, the same roughening solution as described above is used, and the substrate on which the adhesive layer is formed is immersed in the solution, or the roughening solution is sprayed on the substrate. The surface of the adhesive layer can be roughened as a result.

  (iii). Next, electroless plating is performed on the surface-roughened adhesive layer on the substrate. Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless tin plating, electroless gold plating, and electroless silver plating. Particularly, electroless copper plating, electroless nickel plating and It is suitable that it is at least one of electroless gold plating. In addition, after performing the electroless plating, a different kind of electroless plating or electroplating may be performed, or solder may be coated. Furthermore, in providing the metal deposition layer, a method such as electrolytic plating or sputtering may be used in addition to electroless plating. Examples of the metal to be deposited include Cu, Ni, Cr, Ti, Mo, Au, and alloys thereof.

  In the electroless plating, a wiring pattern can be drawn directly by plating by forming a plating resist or the like. Alternatively, electroless plating can be applied to the entire surface and then etched to draw a conductor circuit.

  The printed wiring board obtained as described above includes (i) a single-sided printed wiring board formed by forming a plating resist and a conductor circuit on the substrate via the adhesive layer, and (ii) the adhesive on both sides of the substrate. On a double-sided printed wiring board formed with a plating resist and a conductor circuit through a layer and a through hole, and (iii) a substrate on which a conductor layer is formed (which may have a through hole or a multilayer) There can be mentioned a build-up multilayer wiring board in which conductor circuits are formed in multiple layers via an interlayer insulating layer (via the adhesive layer) having via holes.

( Reference Example 1)
(1) Cresol novolac type epoxy resin (Nippon Kayaku, trade name: EOCN-104S, epoxy equivalent 220, molecular weight 5000) 65 parts by weight, polyethersulfone (PES) (ICI, trade name: Victrex, molecular weight 17000) 40 parts by weight, 5 parts by weight of imidazole curing agent (product name: 2E4MZ-CN, manufactured by Shikoku Kasei) and 20 parts by weight of rubber resin fine powder (made by Nippon Synthetic Rubber) with an average particle size of 5.5 μm After mixing 10 parts by weight of 0.5 μm in diameter, adjust the viscosity to 120 CPS with a homodisper stirrer while adding NMP (normal methylpyrrolidone), then knead with 3 rolls to obtain an adhesive solution It was. At this time, the viscosity at room temperature was 2 to 5 Pa · s.
(2) Apply this adhesive solution on a glass epoxy insulation board (made by Toshiba Chemical Co., Ltd.) with no copper foil attached using a roller coater (manufactured by Thermatronics Trading), and then at 80 ° C for 2 hours. An adhesive layer having a thickness of 20 μm was formed by drying and curing at 120 ° C. for 5 hours and 150 ° C. for 2 hours.
(3) The substrate on which the adhesive layer has been formed is immersed in an aqueous chromic acid solution (CrO ₃ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then neutralized solution (manufactured by Shipley) ) And then washed with water. The roughness of the roughened surface was R _max = 10 μm according to JIS-B-0601.
(4) A palladium catalyst (manufactured by Shipley) is applied to the substrate with the roughened surface of the adhesive layer to activate the surface of the adhesive layer, and then a plating resist is provided according to a conventional method. The printed wiring board was manufactured by immersing it in an additive electroless plating solution having a composition for 11 hours, and performing electroless copper plating with a plating film thickness of 25 μm (see FIG. 1).

When a cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was observed with a TEM, resin particles having an average particle size of 0.1 μm or less were observed.
In addition, a cured product obtained by curing a mixture having a resin composition not mixed with the rubber-based resin fine powder was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. However, there was one peak at the glass transition temperature Tg (see FIG. 2).
Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure (see FIG. 3).

( Reference Example 2)
(1) Cresol novolac epoxy resin (Nippon Kayaku, trade name: EOCN-103S) 70 parts by weight, polyethersulfone (PES) (ICI, trade name: Victrex) 30 parts by weight, imidazole curing agent (Shikoku Kasei Co., Ltd., trade name: 2PHZ-CN) 10 parts by weight and silica spherical fine powder (manufactured by Nippon Shokubai) 20 parts by weight with an average particle diameter of 5.5 μm and 10 parts by weight with an average particle diameter of 0.5 μm Then, while adding NMP solvent, the viscosity was adjusted to 120 CPS with a homodisper stirrer, and then kneaded with three rolls to obtain an adhesive solution.
(2) Apply this adhesive solution on a glass epoxy insulation board (manufactured by Toshiba Chemical Co., Ltd.) with no copper foil attached using a roller coater (manufactured by Thermotronics Trading), and then at 80 ° C. for 3 hours. An adhesive layer having a thickness of 20 μm was formed by drying and curing at 120 ° C. for 3 hours and at 150 ° C. for 5 hours.
(3) The substrate on which the adhesive layer was formed was immersed in hydrofluoric acid at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then immersed in a neutralizing solution (manufactured by Shipley) and then washed with water.
(4) A palladium catalyst (manufactured by Shipley) is applied to the substrate with the roughened surface of the adhesive layer to activate the surface of the adhesive layer, and then a plating resist is provided according to a conventional method. The printed wiring board was manufactured by immersing it in an additive electroless plating solution having a composition for 11 hours, and performing electroless copper plating with a plating film thickness of 25 μm.

A cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this Reference Example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, a resin having an average particle size of 0.05 μm or less Particles were seen.
The cured product obtained by curing the resin composition mixture not mixed with the silica fine powder was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. There was one peak at the glass transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure.

(Example 1 )
(1) A butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin were mixed and then heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN.
(2) Bisphenol A type epoxy resin (Oilized shell, trade name: Epicoat 828, epoxy equivalent 190, molecular weight 380) 70 parts by weight, polyethersulfone (PES) (ICI, trade name: Victrex) 30 parts by weight, After mixing 10 parts by weight of an imidazole-based curing agent (product name; 2E4MZ-CN) and 30 parts by weight of the above epoxy-modified CTBN, the viscosity is adjusted to 120 CPS with a homodisper stirrer while adding an NMP solvent, Subsequently, an adhesive solution was obtained by kneading with three rolls.
(3) Apply this adhesive solution on a glass epoxy insulating board (manufactured by Toshiba Chemical Co., Ltd.) with no copper foil attached using a roller coater (manufactured by Thermatronics Trade), and then at 80 ° C. for 1 hour. An adhesive layer having a thickness of 20 μm was formed by drying and curing at 120 ° C. for 2 hours and at 150 ° C. for 4 hours.
(4) The above substrate on which the adhesive layer has been formed is immersed in a chromic acid aqueous solution (CrO ₃ , 500 g / l) at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then neutralized solution (manufactured by Shipley) ) And then washed with water.
(5) A palladium catalyst (manufactured by Shipley) is applied to the substrate with the roughened surface of the adhesive layer to activate the surface of the adhesive layer, and then a plating resist is provided according to a conventional method. The printed wiring board was manufactured by immersing it in an additive electroless plating solution having a composition for 11 hours, and performing electroless copper plating with a plating film thickness of 25 μm.

A cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, a resin having an average particle size of 0.1 μm or less Particles were seen. In addition, a cured product obtained by curing a mixture having a resin composition not mixed with the rubber resin was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. There was one peak at the glass transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure. Furthermore, when this resin matrix was observed by SEM, the “island structure” of the butadiene-acrylonitrile copolymer resin could be observed in the sea of the resin matrix after being cured. That is, when the surface of the adhesive layer is treated with an oxidizing agent, the island structure is dissolved and removed, and the surface is roughened.

( Reference Example 3 )
Basically, it was the same as Reference Example 1, and the following was used as the adhesive solution. 65 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell, Epicoat 828), 35 parts by weight of polyethersulfone (PES) (trade name; Victrex), imidazole-based curing agent (trade name, manufactured by Shikoku Kasei, 2E4MZ) -CN) 5 parts by weight and rubber resin fine powder (manufactured by Nippon Synthetic Rubber) with 20 parts by weight having an average particle diameter of 5.5 μm and 10 parts by weight with an average particle diameter of 0.5 μm were mixed, and then dimethylformamide / An adhesive solution obtained by adjusting the viscosity to 100 CPS with a homodisper stirrer while adding a butyl cellosolve (1/1) mixed solvent, and then kneading with three rolls.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in the present Reference Example in the same manner as in Reference Example 1 was observed by SEM after observing its cross section with methylene chloride dissolving PES. In addition, a continuous structure (co-continuous structure) of spherical materials considered to be rich in epoxy resin having an average particle diameter of 0.2 to 2 μm was observed.

( Reference Example 4 )
Basically, it was the same as Reference Example 1, and the following was used as the adhesive solution. 50 parts by weight of bisphenol A type epoxy resin (Oilized Shell, Epicoat 828), 50 parts by weight of polyethersulfone (PES) (product name: Victrex), imidazole-based curing agent (product name: 2E4MZ, manufactured by Shikoku Kasei) -CN) 5 parts by weight and 20 parts by weight of rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber) with an average particle diameter of 5.5 μm and 10 parts by weight with an average particle diameter of 0.5 μm were mixed, and then DMF (dimethyl) An adhesive solution obtained by adjusting the viscosity to 100 CPS with a homodisper stirrer while adding formamide) and then kneading with three rolls.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in the present Reference Example in the same manner as in Reference Example 1 was observed by SEM observation of the cross-section with methylene chloride dissolving PES. Sphericals considered to be rich in epoxy resin having an average particle diameter of about 2 to 5 μm were observed.
Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on a PES-rich base (see FIG. 4).

( Reference Example 5 )
(1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper clad laminate (manufactured by Toshiba Chemical Co., Ltd.) and exposed to ultraviolet rays through a mask film on which a desired conductor circuit pattern was drawn, and an image was printed. Next, development was performed with 1,1,1-trichloroethane, and copper in the non-conductor portion was removed using a cupric chloride etching solution, and then the dry film was peeled off with methylene chloride. Thereby, the wiring board which has the 1st layer conductor circuit which consists of a several conductor pattern on a board | substrate was created.
(2) Alumina particles (made by Nippon Light Metal Co., Ltd., trade name: AX34, average particle size 3.9 μm) 200 g in an alumina particle suspension obtained by dispersing in 5 l of acetone while stirring in a Henschel mixer, Obtained by dispersing 300 g of alumina powder (product name: AX34, average particle size: 0.5 μm) in an acetone solution in which epoxy resin (manufactured by Mitsui Petrochemical Co., Ltd.) was dissolved at a ratio of 30 g to 1 l of acetone. By dropping the suspension, the alumina powder was adhered to the surface of the alumina particles, then the acetone was removed, and then heated to 150 ° C. to prepare alumina pseudo particles. The pseudo particles had an average particle diameter of about 4.3 μm, and about 75% by weight was present in the range of ± 2 μm centering on the average particle diameter.
(3) Cresol novolac epoxy resin (Oilized shell, epoxy equivalent 210)
, Molecular weight 2000) 50% acrylate, 70 parts by weight, polyethersulfone (PES) 30 parts by weight, diallyl terephthalate 15 parts by weight, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Mix 4 parts by weight of propanone-1 (Ciba-Geigy), 4 parts by weight of imidazole curing agent (product name: 2E4MZ-CN), and 50 parts by weight of the pseudo alumina particles prepared in (2) above. Then, while adding butyl cellosolve, the viscosity was adjusted to 250 cps with a homodisper stirrer, and then kneaded with three rolls to prepare a photosensitive adhesive solution.
(4) This photosensitive adhesive solution is applied onto the wiring board prepared in (1) above using a roll coater, left in a horizontal state for 20 minutes, and then dried at 70 ° C. to obtain a thickness. A photosensitive adhesive layer of about 50 μm was formed.
(5) A photomask film on which a black circle of 100 μmφ was printed was brought into close contact with the wiring board subjected to the treatment of (4) and exposed with an ultrahigh pressure mercury lamp of 500 mj / cm ² . This was subjected to ultrasonic development treatment with a DMDG (diethylene glycol dimethyl ether) solution to form an opening serving as a via hole of 100 μmφ on the wiring board. Furthermore, the wiring board is exposed at about 3000 mj / cm ² with an ultra-high pressure mercury lamp and heat-treated at 100 ° C. for 1 hour and at 150 ° C. for 5 hours, so that an opening having excellent dimensional accuracy equivalent to that of a photomask film is obtained. The adhesive layer which has was formed.
(6) After the wiring board treated in (5) is treated with hydrofluoric acid, it is immersed in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C. for 15 minutes to cover the surface of the adhesive layer. After roughening, and then immersed in a neutralized solution (manufactured by Shipley), it was washed with water.
(7) A palladium catalyst (manufactured by Shipley) is applied to the substrate with the roughened surface of the adhesive layer to activate the surface of the adhesive layer, and then the additive electroless plating solution having the composition shown in Table 2 is added to the substrate. Electroless copper plating with a plating film thickness of 25 μm was performed by immersion for a period of time.
(8) After repeating the steps (4) to (7) twice, the above step (1) is further performed to manufacture a build-up multilayer wiring board having four wiring layers (FIG. 5). reference).

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was etched with methylene chloride in the cross section and observed by SEM. The average particle size was 0.2-2 μm. A continuous structure (co-continuous structure) of spherical materials considered to be rich in epoxy resin was observed (see FIG. 6).
Moreover, the cured product obtained by curing the mixture of the resin composition not mixed with the alumina pseudo particles was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. There were two peaks of the glass transition temperature Tg (see FIG. 7).
Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a co-continuous structure.

( Reference Example 6 )
(1) A photosensitive dry film (manufactured by DuPont) was laminated on a glass epoxy copper clad laminate (manufactured by Toshiba Chemical Co., Ltd.) and exposed to ultraviolet rays through a mask film on which a desired conductor circuit pattern was drawn, and an image was printed. Next, development was performed with 1,1,1-trichloroethane, and copper in the non-conductor portion was removed using a cupric chloride etching solution, and then the dry film was peeled off with methylene chloride. Thereby, the wiring board which has the 1st layer conductor circuit which consists of a several conductor pattern on a board | substrate was created.
(2) Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole type curing agent (25% of epoxy group of cresol novolak type epoxy resin dissolved in DMDG (diethylene glycol dimethyl ether)) Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), photosensitive monomer acrylated isothiocyanate (manufactured by Toa Gosei, trade name: Aronix M215), photoinitiator (Ciba Geigy, trade name: I-907), The following composition is mixed using an NMP solvent. Further, 20 parts by weight of a rubber-based resin fine powder (manufactured by Nippon Synthetic Rubber) with an average particle size of 5.5 μm and 10 with an average particle size of 0.5 μm are mixed into this mixture. After mixing parts by weight, the viscosity was adjusted to 120 CPS with a homodisper stirrer, and then kneaded with three rolls to obtain a photosensitive adhesive solution.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 75/25/10/5/5/5
(3) This photosensitive adhesive solution is the above-mentioned (1)
It was applied on the wiring board prepared in (1) using a roll coater, left in a horizontal state for 20 minutes, and then dried at 60 ° C.
(4) A photomask film printed with a black circle of 100 μmφ was brought into close contact with the wiring board subjected to the treatment of (3) and exposed with an ultra-high pressure mercury lamp of 500 mj / cm ² . By subjecting this to ultrasonic development with a DMDG solution, an opening to be a via hole of 100 μmφ was formed on the wiring board. Furthermore, the wiring board is exposed at about 3000 mj / cm ² with an ultra-high pressure mercury lamp and heat-treated at 100 ° C. for 1 hour and at 150 ° C. for 5 hours, so that an opening having excellent dimensional accuracy equivalent to that of a photomask film is obtained. An adhesive layer having a thickness of 50 μm was formed.
(5) The surface of the adhesive layer is roughened by immersing the wiring board treated in (4) above in potassium permanganate (KMnO ₄ , 500 g / l) at 70 ° C. for 15 minutes, and then neutralizing. It was immersed in a solution (made by Shipley) and then washed with water.
(6) A palladium catalyst (manufactured by Shipley) is applied to the substrate with the roughened surface of the adhesive layer to activate the surface of the adhesive layer, and then the additive electroless plating solution having the composition shown in Table 2 is added to the substrate. Electroless copper plating with a plating film thickness of 25 μm was performed by immersion for a period of time.
(7) After the steps (3) to (6) were repeated twice, the step (1) was further performed to produce a build-up multilayer wiring board having four wiring layers.

Only the resin corresponding to the resin matrix of the adhesive used in this Example, drying under the above conditions, UV curable, thermoset cured product obtained is was similarly TEM observation as in Reference Example 1, the average particle Resin particles having a diameter of 0.1 μm or less were observed. In addition, a cured product obtained by curing a mixture having a resin composition not mixed with the rubber resin fine powder was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. However, there was one peak at the glass transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure (see FIG. 3). 8 and 9 show SEM cross-sectional photographs of the adhesive layer before and after curing, respectively.

( Reference Example 7 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (product name: 2E4MZ-CN), acrylated with 25% of the epoxy group of cresol novolac epoxy resin A photosensitive monomer, acrylated isothiocyanate (product name: Aronix M215, manufactured by Toa Gosei Co., Ltd.), photoinitiator (product name: I-907), NMP (dimethylformamide) with the following composition: Further, 20 parts by weight of rubber resin fine powder (manufactured by Nippon Synthetic Rubber) with an average particle diameter of 5.5 μm and 10 parts by weight with an average particle diameter of 0.5 μm are mixed with this mixture. A photosensitive adhesive solution obtained by adjusting the viscosity to 120 CPS with a disper stirrer and then kneading with three rolls.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 75/25/10/5/5
The adhesive was cured by drying at 80 ° C., UV curing, and then thermosetting.

The cured product obtained by drying and curing only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was etched with methylene chloride and observed by SEM. A continuous structure (co-continuous structure) of spherical materials considered to be rich in 2 μm epoxy resin was observed.

( Reference Example 8 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (product name: 2E4MZ-CN), acrylated with 25% of the epoxy group of cresol novolac epoxy resin A photosensitive monomer acrylated isothiocyanate (product name: Aronix M215, manufactured by Toa Gosei Co., Ltd.) and photoinitiator (product name: I-907), mixed using NMP with the following composition, After mixing 20 parts by weight of a rubber-based resin fine powder having an average particle diameter of 5.5 μm and 10 parts by weight of an average particle diameter of 0.5 μm to this mixture, the viscosity was adjusted to 120 CPS with a homodisper stirrer, and then A photosensitive adhesive solution obtained by kneading with three rolls.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 75/25/10/5/5
The adhesive was cured by drying at 100 ° C., UV curing, and then thermosetting.

The cured product obtained by drying and curing only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was etched with methylene chloride in which PES was dissolved and observed by SEM. Sphericals considered to be rich in epoxy resin having a particle size of about 2 to 5 μm were observed.
Moreover, this resin matrix has a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on a PSF-rich base.

As in Reference Example 6 to Example 8 described above, by varying the drying conditions, quasi-homogeneous phase dissolution structure from the adhesive of the same composition, co-continuous structure, that the cured product of the spherical domain structure is obtained was found.
This is because, in the case of a photosensitive adhesive, if it has a uniform structure at the time of drying, it is quickly cured by photocuring, and therefore phase separation due to subsequent thermal curing is relatively unlikely to occur.
For reference, phase diagrams are shown in FIGS. These phase diagrams are different from those in Reference Examples 6 to 8 except that the preparation conditions of the adhesive were different, and were performed using sensitized epoxy / PES / TMPTA / I-907 / imidazole = 75/25/20/5/5. .

( Reference Example 9 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Cresole novolak-type epoxy resin (Oilized Shell) 100% acrylated photosensitive epoxy oligomer, PES, imidazole curing agent (product name: 2E4MZ-CN), acrylic acrylic monomer Isothiocyanate (product of Toa Gosei, trade name: Aronix M215), photoinitiator (product of Ciba Geigy, trade name: I-907), mixed with NMP with the following composition, and further rubber based on this mixture After mixing 20 parts by weight of resin fine powder (made of Japan synthetic rubber) with an average particle size of 5.5 μm and 10 parts by weight with an average particle size of 0.5 μm, the viscosity is adjusted to 120 CPS with a homodisper stirrer, and then A photosensitive adhesive solution obtained by kneading with three rolls.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 80/20/10/5/5

The resin obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this Reference Example in the same manner as in Reference Example 6 was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Resin particles were seen.
In addition, a cured product obtained by curing a mixture having a resin composition not mixed with the rubber resin fine powder was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. However, there was one peak at the glass transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure (see FIG. 3).

( Reference Example 10 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Photosensitive epoxy oligomer with 100% acrylated epoxy group of cresol novolac type epoxy resin (Oilized Shell), phenoxy resin, imidazole-based curing agent (product name: 2E4MZ-CN), photosensitive monomer Acrylic isothiocyanate (manufactured by Toa Gosei Co., Ltd., trade name: Aronix M215) and photoinitiator (manufactured by Ciba Geigy, trade name: I-907) were mixed using DMF with the following composition. After mixing 30 parts by weight of an agglomerated rubber-based resin fine powder having a particle size of 3.5 μm (refer to the manufacturing method disclosed in Example 1 of JP-A-1-301775), adding a DMF solvent, A photosensitive adhesive solution obtained by adjusting the viscosity to 120 CPS with a homodisper stirrer and then kneading with three rolls.
Resin composition: Photosensitized epoxy / phenoxy / M215 / I-907 / imidazole
= 79/30/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this Reference Example in the same manner as in Reference Example 6 was etched with 2-butanone in which the phenoxy resin was dissolved, and observed by SEM. As a result, a continuous structure (co-continuous structure) of spherical materials considered to be rich in epoxy resin having an average particle diameter of 0.2 to 2 μm was observed.

( Reference Example 11 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Cresole novolak-type epoxy resin (manufactured by Yuka Shell) 100% acrylated photosensitive epoxy oligomer, PSF, imidazole curing agent (product name: 2E4MZ-CN), acrylic monomer Isothiocyanate (product of Toa Gosei, trade name: Aronix M215), photoinitiator (product of Ciba Geigy, trade name: I-907), and mixed with DMF with the following composition. After mixing 30 parts by weight of an agglomerated rubber-based resin fine powder having a diameter of 3.5 μm (refer to the production method disclosed in Example 1 of JP-A-1-301775), homopolymers were added while adding a DMF solvent. A photosensitive adhesive solution obtained by adjusting the viscosity to 120 CPS with a disper stirrer and then kneading with three rolls.
Resin composition: Photosensitized epoxy / PSF / M215 / I-907 / imidazole
= 60/40/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in the present Reference Example in the same manner as in Reference Example 6 was observed by SEM observation of the cross-section with methylene chloride dissolving PSF. Sphericals considered to be rich in epoxy resin having an average particle diameter of about 2 to 5 μm were observed. Moreover, this resin matrix has a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on a PSF-rich base.

( Reference Example 12 )
Basically, it was the same as in Reference Example 4 , and the rubber-based resin fine powder was zirconia (manufactured by Nippon Shokubai Chemical Industry, trade name: NS-OY-S), and the roughening solution was hydrofluoric acid. The resin structure of the adhesive resin matrix used in this reference example was a spherical domain structure.
( Reference Example 13 )
Basically, it was the same as Reference Example 7 , the rubber-based resin fine powder was magnesia (trade name; MTK-30, manufactured by Iwatani Chemical Industries), and the roughening solution was 6N hydrochloric acid. The resin structure of the resin matrix of the adhesive used in this reference example was a co-continuous structure.
( Reference Example 14 )
Basically, it was the same as Reference Example 8 , the rubber-based resin fine powder was aluminum hydroxide (manufactured by Nippon Light Industry Co., Ltd., trade name: B103 · T), and the roughening solution was an aqueous ammonia solution. The resin structure of the adhesive resin matrix used in this reference example was a spherical domain structure.

(Example 2 )
Basically, it was the same as Reference Example 3, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture was heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN, and 30 parts by weight of this resin liquid was mixed with a bisphenol A type epoxy resin (oil 65 parts by weight manufactured by Kasei Shell, Epicoat 828), 35 parts by weight polyethersulfone (PES) (trade name; Victrex), 5 parts by weight imidazole curing agent (trade name; 2E4MZ-CN, manufactured by Shikoku Kasei) After mixing, an adhesive solution obtained by adjusting the viscosity to 100 CPS with a homodisper stirrer while adding a mixed solvent of dimethylformamide / butyl cellosolve (1/1), and then kneading with three rolls.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Reference Example 3 was etched with methylene chloride in which PES was dissolved and observed by SEM. In addition, a continuous structure (co-continuous structure) of spherical materials considered to be rich in epoxy resin having an average particle diameter of 0.2 to 2 μm was observed. Further, when this resin matrix was observed with an SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 3 )
Basically, it was the same as Reference Example 4, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture was heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN, and 30 parts by weight of this resin liquid was mixed with a bisphenol A type epoxy resin (oil 50 parts by weight manufactured by Kasei Shell, Epicoat 828), 50 parts by weight of polyethersulfone (PES) (trade name; Victrex), 5 parts by weight of imidazole curing agent (product name: 2E4MZ-CN) manufactured by Shikoku Kasei After mixing, an adhesive solution obtained by adjusting the viscosity to 100 CPS with a homodisper stirrer while adding DMF and then kneading with three rolls.

A cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Reference Example 4 was etched with methylene chloride in which PES was dissolved and observed by SEM. Sphericals considered to be rich in epoxy resin having an average particle diameter of about 2 to 5 μm were observed.
Moreover, this resin matrix had a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on a PES-rich base (see FIG. 4). Further, when this resin matrix was observed with an SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 4 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. After mixing a butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin, the mixture was heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole curing agent (trade name; 2E4MZ-CN), photosensitive monomer Acrylic isothiocyanate (product name: Aronix M215 manufactured by Toa Gosei Co., Ltd.), photoinitiator benzophenone (BP) (manufactured by Kanto Chemical), photosensitizer Michler ketone (manufactured by Kanto Chemical), and NMP with the following composition The viscosity was adjusted to 120 CPS with a homodisper stirrer, and then the contact obtained by kneading with three rolls. Agent solution.
Resin composition: Photosensitized epoxy / PES / M215 / BP / imidazole
= 75/25/10/5 / 0.5 / 5

A cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Reference Example 6 was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm. The following resin particles were observed. In addition, a cured product obtained by curing a mixture having a resin composition not mixed with the rubber resin was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. There was one peak at the glass transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this example exhibits a quasi-homogeneous compatible structure (see FIG. 3).
Furthermore, when this resin matrix was observed by SEM, the “island structure” of the butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 5 )
Basically, it was the same as Reference Example 7, and the following was used as the adhesive solution. A butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin were mixed and then heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN. A cresol novolak type in which 30 parts by weight of this resin solution was dissolved in DMDG. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (product name: 2E4MZ-CN), photosensitivity, acrylated with 25% of the epoxy group of epoxy resin The monomer acrylated isothiocyanate (product name: Aronix M215, manufactured by Toa Gosei Co., Ltd.) and photoinitiator (product name: I-907), mixed with DMF with the following composition, and homodisper stirrer An adhesive solution obtained by adjusting the viscosity to 120 CPS and then kneading with three rolls.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 75/25/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Reference Example 7 was etched with methylene chloride and observed by SEM. A continuous structure (co-continuous structure) of spherical materials thought to be rich in epoxy resin of 0.2 to 2 μm was observed. Further, when this resin matrix was observed with an SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

(Example 6 )
Basically, it was the same as Reference Example 8, and the following was used as the adhesive solution. A butadiene-acrylonitrile copolymer oligomer (CTBN) and a bisphenol A type epoxy resin were mixed and then heated at 160 ° C. for 2 hours to obtain an epoxy-modified CTBN, and 30 parts by weight of this resin solution was added to the epoxy of a cresol novolac type epoxy resin. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (manufactured by Shikoku Kasei Co., Ltd., trade name: 2E4MZ-CN), acrylic acrylic monomer Isothiocyanate (product of Toa Gosei, trade name: Aronix M215), photoinitiator (product of Ciba Geigy, trade name: I-907), mixed with DMF with the following composition, and adjusted to a viscosity of 120 CPS with a homodisper stirrer Subsequently, an adhesive solution obtained by kneading with three rolls.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 75/25/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this example in the same manner as in Reference Example 8 was observed by SEM after etching the cross section with methylene chloride dissolving PES. Sphericals considered to be rich in epoxy resin having an average particle diameter of about 2 to 5 μm were observed. Moreover, this matrix resin has a so-called sea-island structure (spherical domain structure) in which epoxy-rich spheres floated on a PSF-rich base. Further, when this resin matrix was observed with an SEM, an “island structure” of a butadiene-acrylonitrile copolymer rubber resin was observed in the sea of the resin matrix.

( Reference Example 15 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole curing agent (trade name; 2E4MZ-CN) manufactured by Shikoku Kasei Co., Ltd. A photosensitized acrylated isothiocyanate (product name: Aronix M215, manufactured by Toa Gosei Co., Ltd.) and photoinitiator (product name: I-907), mixed using DMF with the following composition, After mixing 25 parts by weight of the epoxy-terminated silicone resin with the mixture, the viscosity was adjusted to 120 CPS with a homodisper stirrer, and then kneaded with three rolls to obtain an adhesive solution.
Resin composition: Photosensitized epoxy / PES / M215 / I-907 / imidazole
= 70/30/10/5/5

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this Reference Example in the same manner as in Reference Example 6 was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Of resin particles were observed. Further, the cured product obtained by curing a mixture having a resin composition not mixed with the epoxy group-terminated silicone resin was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. However, there was one peak at the glass transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure.

( Reference Example 16 )
(1) Cresol novolac epoxy resin (Nippon Kayaku, trade name: EOCN-104S
, Epoxy equivalent 220, molecular weight 5000) 65 parts by weight, polyethersulfone (PES) (manufactured by ICI, trade name: Victrex, molecular weight 17000) 40 parts by weight, imidazole curing agent (manufactured by Shikoku Kasei, trade name: 2E4MZ-CN) After mixing 5 parts by weight and 20 parts by weight of a melamine resin powder having a low crosslinking degree with an average particle diameter of 5.5 μm and 10 parts by weight with an average particle diameter of 0.5 μm, add NMP and mix with a homodisper stirrer The viscosity was adjusted to 120 CPS, and then kneaded with three rolls to obtain an adhesive solution. At this time, the viscosity at room temperature was 2 to 5 Pa · s.
(2) Apply the adhesive solution to both sides of the glass epoxy substrate, leave it in a horizontal state for 20 minutes, then dry at 60 ° C, heat cure at 100 ° C for 1 hour, and 150 ° C for 5 hours to obtain a thickness A resin adhesive layer of about 50 μm was formed.
(3) The substrate having this double-sided adhesive layer was allowed to stand in 121 ° C., 2 atm, saturated water vapor for 2 hours to decompose and remove the melamine resin powder on the surface of the adhesive layer. Electron microscope (SEM) photographs before and after the decomposition removal are shown in FIGS. As is apparent from these photographs, the melamine resin is reduced by decomposition.
(4) A palladium catalyst (manufactured by Shipley Co., Ltd.) is applied to the substrate with the roughened surface of the resin insulation layer to activate the surface of the insulation layer, and then immersed in an electroless copper plating solution for 11 hours. Electroless copper plating with a thickness of 25 μm was applied to obtain a double-sided copper-clad laminate.
(5) A through hole was made in this double-sided copper-clad laminate.
(6) After providing a palladium nucleus (manufactured by Shipley Co., Ltd.), a photoresist was pasted, exposed and developed to form a plating resist.
(7) According to a conventional method, electroless copper plating was performed, and further electrolytic copper plating was performed to form a conductor circuit portion.
(8) After removing the plating resist, etching with ferric chloride was performed to remove the copper film between the patterns, and a printed wiring board was manufactured.

A cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Resin particles were seen. Moreover, when the cured product obtained by curing the resin composition mixture not mixed with the melamine resin powder was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min, There was one peak at the glass transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure (see FIG. 3).

( Reference Example 17 )
Basically, it was the same as Reference Example 6, and the following was used as the adhesive solution. Photosensitized epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (trade name, manufactured by Shikoku Kasei Co., Ltd.) obtained by acrylated 25% of the epoxy group of cresol novolac type epoxy resin dissolved in DMDG 2E4MZ-CN), photosensitive monomer acrylated isothiocyanate (product of Toa Gosei, trade name; Aronix M215), photoinitiator benzophenone (BP) (manufactured by Kanto Chemical), photosensitizer Michler ketone (manufactured by Kanto Chemical) An adhesive solution obtained by further adding cellulose acetate butyrate powder, mixing with NMP with the following composition, adjusting the viscosity to 120 CPS with a homodisper stirrer, and then kneading with three rolls.
Resin composition: Photosensitized epoxy / PES / M215 / BP / imidazole
= 75/25/10/5 / 0.5 / 5
Moreover, the roughening conditions of this reference example were performed by immersing in 1M sodium hydroxide aqueous solution of 80 degreeC, and hydrolyzing a cellulose acetate butyrate.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this Reference Example in the same manner as in Reference Example 6 was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Of resin particles were observed. Further, a cured product obtained by curing a mixture having a resin composition not mixed with the rubber resin was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. There was one peak at the transition temperature Tg.
Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure.

Peel strength of the electroless copper plated film in the printed wiring board produced in Reference Example 1 to 17 and Examples 1-6, as well as to measure the insulation resistance and glass transition temperature T _g of the interlayer resin insulating layer. Furthermore, a heat cycle test of −65 ° C. × 30 min to 125 ° C. × 30 min was performed. The results are shown in Table 3.
As is apparent from the results shown in this table, by using the adhesive of the present invention in which the resin composite showing a pseudo-homogeneous phase dissolution structure, a co-continuous structure, and a spherical domain structure is used as a resin matrix, adhesive strength, insulation, A printed wiring board having significantly improved heat resistance and heat cycle characteristics compared to conventional ones can be produced.

The peel strength, insulation resistance, glass transition temperature Tg, and heat cycle test method or evaluation method will be described.
(1) Peel strength JIS-C-6481
(2) Insulation resistance An interlayer insulation layer was formed on the substrate, roughened and then provided with a catalyst, and then a plating resist was formed to form a resist pattern. Thereafter, electroless plating was performed, and the insulation resistance between patterns was measured. In addition, the insulation between patterns measured the value 1000 hours after 80 degreeC / 85% / 24V in the comb pattern of L / S = 75/75 micrometer.
(3) Glass transition temperature Tg
It was measured by dynamic viscoelasticity measurement.
(4) Heat cycle test A heat cycle test of −65 ° C. × 30 min to 125 ° C. × 30 min was conducted to investigate the occurrence of cracks and the presence or absence of delamination of the interlayer insulating layer, and the durability cycle number was evaluated.

( Reference Example 18 ): Metallic melamine decorative board
In Reference Example 1 to 17 and Examples 1 to 6 has been described an example about the printed circuit board, this reference example, an example of application to the decorative board of the present invention.
(1) A wood pulp fiber papermaking paper having a basis weight of 10 to 80 g / m ² was impregnated with a melamine resin and dried to obtain an impregnated paper having a thickness of 100 μm.
(2) Cresol novolac type epoxy resin (Nippon Kayaku, trade name: EOCN-104S, epoxy equivalent 220, molecular weight 5000) 65 parts by weight, polyethersulfone (PES) (ICI, trade name: Victrex, molecular weight 17000) 40 parts by weight, 5 parts by weight of an imidazole-based curing agent (trade name; 2E4MZ-CN, manufactured by Shikoku Kasei) and 20 parts by weight of calcium carbonate fine powder having an average particle size of 5.5 μm and 10 parts having an average particle size of 0.5 μm After mixing parts by weight, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding a dimethylformamide / butyl cellosolve (1/1) mixed solvent, and then kneaded with three rolls to obtain an adhesive solution. At this time, the viscosity at room temperature was 2 to 5 Pa · s.
(3) Apply the adhesive obtained in (2) above to the surface of the plywood board, then vacuum dry at 30 ° C, heat at 80 ° C for 2 hours, 120 ° C for 5 hours, and 150 ° C for 2 hours. Curing was performed to form an adhesive layer having a thickness of 20 μm.
(4) This adhesive layer is immersed in 6N hydrochloric acid at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, then immersed in a neutralizing solution (made by Shipley), washed with water, and R _max = 10 ± A 5 μm adhesive layer was obtained.
(5) Activate the surface of the adhesive layer by applying a palladium catalyst (made by Shipley) to the substrate with the roughened surface of the adhesive layer. A 60 μm silver layer was formed.
(6) The melamine resin-impregnated paper obtained in (1) above was laminated as an overlay paper on the surface of this silver layer.
(7) Furthermore, the overlay paper is laminated on this overlay paper by laminating a shaping plate having 1-60 μm irregularities and thermocompression bonding at 130-170 ° C. under a pressure of 30-80 kg / cm ^2. In addition, the surface was embossed to obtain a melamine decorative board having a metallic luster.

  Since the melamine decorative board obtained in this way is formed of a melamine resin layer having a light-transmitting and uneven surface, the unevenness acts as a lens to lift the lower silver layer, and the silver gloss Shines and is excellent in design. And when the heat cycle test of -65 degreeC * 30min-125 degreeC * 30min was done with respect to this decorative board, neither a crack nor peeling was seen.

The cured product obtained by thermosetting only the resin corresponding to the resin matrix of the adhesive used in this Reference Example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Of resin particles were observed. The cured product obtained by curing the resin composition mixture not mixed with the calcium carbonate fine powder was subjected to a viscoelasticity measurement test under conditions of a vibration frequency of 6.28 rad / sec and a temperature increase rate of 5 ° C./min. There was one peak at the glass transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

Reference Example 19 : Plating-coated gear This reference example is an application example to the plating-coated gear of the present invention.
(1) A gear-shaped molded body was produced using polyimide in accordance with a conventional method.
(2) Sensitive epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (manufactured by Shikoku Kasei), acrylated 25% of the epoxy group of cresol novolac epoxy resin dissolved in DMDG 2E4MZ-CN), caprolactone-modified trisisocyanurate (product of Toa Gosei Co., Ltd., trade name: Aronix M315), photoinitiator benzophenone (BP), photosensitizer Michler's ketone with the following composition: After mixing with NMP, in addition to this, 30 parts by weight of rubber filler (Nippon Gosei Co., Ltd.) with an average particle size of 5.0 μm was mixed, and then adjusted to a viscosity of 1000 CPS with a homodisper stirrer, followed by 3 An adhesive solution was obtained by kneading with this roll.
Resin composition: Photosensitized epoxy / PES / M315 / BP / imidazole
= 70/30/10/5 / 0.5 / 5
(3) After applying the adhesive prepared in (2) above to the gear-shaped molded body prepared in (1) above, vacuum-drying at 25 ° C., UV-curing this, and further heat-curing Then, an adhesive layer made of a resin matrix showing a pseudo-homogeneous compatible structure was formed.
(4) Next, the surface of the adhesive layer was roughened by immersing in an aqueous chromic acid solution (CrO ₃ , 500 g / l) at 70 ° C. for 15 minutes, immersed in a neutralized solution (manufactured by Shipley), and then washed with water. The roughened surface was JIS-B-0601R _max = 10 μm.
(5) After the surface of the adhesive layer is roughened, a palladium catalyst (made by Shipley) is applied to activate the surface of the adhesive layer, and then nickel-phosphorous plating is performed according to a conventional method to increase the metallic luster. Made a gear with.

  The gear thus obtained is resistant to chemicals such as acids and has a hard surface, so it has excellent wear resistance. The use of the gear did not cause the nickel layer on the surface to peel off. Moreover, the stress associated with the use of the gear did not cause cracks in the adhesive layer, and the nickel plating did not peel off.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Resin particles were seen. Further, a cured product obtained by curing a mixture of a resin composition not mixed with the rubber filler was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. There was one peak at the transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure.

Reference Example 20 : Semiconductor Mounted Substrate with Heat Sink This reference example is an application example to the semiconductor mounted substrate with a heat sink of the present invention.
(1) Sensitive epoxy oligomer (CNA25, molecular weight 4000), PES (molecular weight 17000), imidazole-based curing agent (manufactured by Shikoku Chemicals Co., Ltd.) in which 25% of the epoxy group of cresol novolac type epoxy resin dissolved in DMDG is acrylated 2E4MZ-CN), caprolactone-modified trisisocyanurate (product of Toa Gosei Co., Ltd., trade name: Aronix M315), photoinitiator benzophenone (BP), photosensitizer Michler's ketone with the following composition: Mix with NMP, and in addition to this, mix 30 parts by weight of aluminum nitride powder with an average particle size of 5.0 μm, adjust the viscosity to 1000 CPS with a homodisper stirrer, and then knead with three rolls Thus, an adhesive solution was obtained.
Resin composition: Photosensitized epoxy / PES / M315 / BP / imidazole
= 70/30/10/5 / 0.5 / 5
(2) Apply the adhesive solution of (1) above to the base material of a semiconductor mounting substrate consisting of an aluminum substrate and a lead frame, vacuum dry at 25 ° C., UV cure this, and then heat cure The aluminum substrate was covered with the adhesive layer, and at the same time, the aluminum substrate and the lead frame were integrated to form an adhesive layer made of a resin matrix having a pseudo-homogeneous compatible structure.
(3) The semiconductor mounting substrate having the adhesive layer formed thereon was immersed in water to dissolve and remove the aluminum nitride powder present on the surface of the adhesive layer, thereby roughening the adhesive layer.
(4) Attaching a plating resist film, exposing and developing to form a plating resist, performing electroless copper plating, forming a conductor circuit on the surface, and making electrical connection with the lead frame by the conductor circuit It was.
(5) After mounting the IC chip, resin-sealing by potting and casing, a semiconductor mounting substrate with a heat sink was manufactured.

  The semiconductor mounting substrate with a heat sink thus obtained had good heat dissipation because of the high thermal conductivity of aluminum nitride. In addition, the resin matrix of the present example decomposes terminal functional groups under high temperature, high humidity, and high pressure conditions to generate organic acids such as acetic acid and formic acid, while aluminum nitride is ammonia under the above conditions. Since the decomposition occurs while generating acid, the acid can be neutralized and corrosion of the deposited metal can be suppressed.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Resin particles were seen. Further, the cured product obtained by curing the resin composition mixture not mixed with aluminum nitride was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. There was one peak at the transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this reference example has a pseudo-homogeneous compatible structure.

( Reference Example 21 ); Electromagnetic Interference Wave (EMI) Plating Film Shield This reference example is an application example of the present invention to an electromagnetic interference wave (EMI) plating film shield.
(1) Cresol novolac type epoxy resin (Nippon Kayaku, trade name: EOCN-104S, epoxy equivalent 220, molecular weight 5000) 65 parts by weight, polyethersulfone (PES) (ICI, trade name: Victrex, molecular weight 17000) 40 parts by weight, 5 parts by weight of an imidazole curing agent (trade name; 2E4MZ-CN, manufactured by Shikoku Kasei) and 20 parts by weight of nickel fine powder having an average particle diameter of 5.5 μm and 10 parts by weight having an average particle diameter of 0.5 μm After mixing the parts, the viscosity was adjusted to 120 CPS with a homodisper stirrer while adding a dimethylformamide / butyl cellosolve (1/1) mixed solvent, followed by kneading with a three roll to obtain an adhesive solution. At this time, the viscosity at room temperature was 2 to 5 Pa · s.
(2) This adhesive solution is applied to filter paper using a roller coater (manufactured by Thermatronics Trading), then dried and cured at 80 ° C. for 2 hours, 120 ° C. for 5 hours, and 150 ° C. for 2 hours. An adhesive layer having a thickness of 20 μm was formed.
(3) The filter paper on which the adhesive layer was formed was immersed in hydrochloric acid at 70 ° C. for 15 minutes to roughen the surface of the adhesive layer, and then immersed in a neutralization solution (manufactured by Shipley) and then washed with water. The roughened surface was JIS-B-0601R _max = 10 μm.
(4) A palladium catalyst (manufactured by Shipley) was applied to the substrate with the roughened surface of the adhesive layer to activate the surface of the adhesive layer, and then nickel plating was performed according to a conventional method.

  The electromagnetic interference (EMI) shielding material thus obtained contains nickel in the adhesive itself, and the plating film also has a shielding effect. Since these have a multi-layer structure, the shielding properties are improved. Are better. Moreover, even if the shield material is bent, cracks do not occur in the adhesive layer, and the processing of the shield material is facilitated.

The cured product obtained by curing only the resin corresponding to the resin matrix of the adhesive used in this reference example under the above conditions was observed by TEM in the same manner as in Reference Example 1. As a result, the average particle size was 0.1 μm or less. Resin particles were seen. Further, the cured product obtained by curing the resin composition mixture not mixed with the nickel fine powder was subjected to a viscoelasticity measurement test under the conditions of a vibration frequency of 6.28 rad / sec and a heating rate of 5 ° C./min. There was one peak at the glass transition temperature Tg. Therefore, it is considered that the resin matrix of the adhesive used in this example has a pseudo-homogeneous compatible structure.

( Reference Example 22 ); Screw
(1) A screw-shaped substrate was molded from polycarbonate.
(2) Cresol novolac epoxy resin (Nippon Kayaku, trade name; EOCN-104S, epoxy equivalent 220, molecular weight 5000) 65 parts by weight, polyethersulfone (PES) (ICI, trade name; Victrex, molecular weight 17000) 40 parts by weight, 5 parts by weight of an imidazole-based curing agent (product name; 2E4MZ-CN, manufactured by Shikoku Kasei) and 20 parts by weight of vinyl chloride resin powder having an average particle size of 5.5 μm and 10 parts having an average particle size of 0.5 μm After mixing parts by weight, the mixture was stirred with a homodisper stirrer and then kneaded with three rolls to obtain an adhesive solution.
(3) The screw-shaped substrate of (1) above is immersed in this adhesive solution, and then dried and cured at 80 ° C. for 2 hours, 120 ° C. for 5 hours, and 150 ° C. for 2 hours to a thickness of 20 μm. An adhesive layer was formed. The cured adhesive layer had a spherical domain structure as a result of SEM observation of the fracture surface etched with methylene chloride.
(4) Next, it was immersed in acetone to dissolve and remove the vinyl chloride resin powder on the surface of the adhesive layer, thereby roughening the surface of the adhesive layer.
(5) A palladium catalyst (manufactured by Shipley) was applied to the surface of the adhesive layer to activate the surface of the adhesive layer, and then electroless silver plating was performed according to a conventional method to produce a screw.

  Since the surface of the screw thus obtained is silver, algae and the like are difficult to adhere due to the sterilization action of silver, and the base is an integral molding of polycarbonate, so that it breaks due to the centrifugal force of rotation. Hateful. Moreover, since the normal screw is cut from the metal lump by cutting, the cost is high, but the screw of the present embodiment can be integrally formed with resin, so that the cost can also be reduced. Furthermore, since the adhesive layer has toughness, cracks do not occur due to distortion caused by rotation.

It is a manufacturing process figure which shows one Example of the printed wiring board concerning invention. It is a figure which shows the dynamic viscoelasticity measurement result of the resin composite which shows the pseudo-homogeneous compatible structure concerning invention. It is a TEM photograph of the crystal structure which shows the pseudo-homogeneous compatible structure of the resin composite concerning invention. It is a SEM photograph of the crystal structure which shows the spherical domain structure of the resin composite concerning invention. It is another manufacturing process figure which shows one Example of the printed wiring board using the resin composite concerning invention. It is a SEM photograph of the crystal structure which shows the co-continuous structure of the resin composite concerning invention. It is a figure which shows the dynamic viscoelasticity measurement result of the resin composite which shows the co-continuous structure concerning invention. It is a SEM photograph which shows the crystal structure of the adhesive bond layer cross section before hardening after drying. It is a SEM photograph which shows the crystal structure of the adhesive bond cross section after hardening. FIG. 4 is a phase diagram showing the relationship between the drying temperature of the CNA25 / PES / TMPTA-based mixture and the state of the cured resin composite. It is a phase diagram which shows the relationship between the drying temperature of a CNA25 / PES type mixture, and the state of the resin composite after hardening. It is a phase diagram which shows the relationship between the drying temperature of an epoxy / PES type mixture, and the state of the resin composite after hardening. It is a SEM photograph which shows the crystal structure of the adhesive bond layer cross section which shows the state before decomposition | disassembly of the particle | grains (low polymerization degree melamine resin) which can be decomposed | disassembled. It is a SEM photograph which shows the crystal structure of the adhesive bond layer cross section which shows the state after decomposition | disassembly of the particle | grains (low polymerization degree melamine resin) which can be decomposed | disassembled.

Explanation of symbols

1 Substrate 2 Adhesive layer 3 Resist 31 Dry film 4, 6, 8, 10 Conductor 5 Via hole

Claims (2)

An epoxy-modified CTBN resin that is compatible with the heat-resistant resin matrix before curing in the uncured heat-resistant resin matrix, phase-separated from the heat-resistant resin matrix after curing, and can be dissolved and removed by an acid or an oxidizing agent. In an adhesive made by mixing liquids,
The heat-resistant resin matrix is composed of a resin mixture of an epoxy resin as a thermosetting resin and / or an epoxy acrylate as a photosensitive resin and a polyether sulfone as a thermoplastic resin, and the resin mixture is subjected to a curing treatment to form a resin. The compatibility is adjusted so as to form a composite and to disperse the dissolved and removable CTBN resin into islands in the sea of the heat-resistant resin matrix made of the cured resin composite. An adhesive for printed wiring boards. In a method for producing an adhesive layer having a roughened surface for a printed wiring board,
A heat-resistant resin matrix comprising the cured resin composite by curing the adhesive for printed wiring boards according to claim 1 provided on a substrate for printed wiring boards , wherein the dissolution and removal are possible. A CTBN resin is dispersed in islands in the sea of the heat-resistant resin matrix to form a heat-resistant resin matrix that forms a sea-island structure;
A method for producing an adhesive layer for a printed wiring board, comprising forming the roughened surface by dissolving and removing the CTBN resin from the surface of a heat-resistant resin matrix comprising the cured resin composite.

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